Tuning acceptor content and molecular structure in linear donor–acceptor polymeric photocatalysts for ultrahigh-performance visible-light-driven hydrogen evolution

A series of linear conjugated polymers were synthesized by tuning the dibenzothiophene-S,S-dioxide (DBTO) content and varying their molecular structures, and applied to study the light-driven hydrogen generation from water. We found that the photocatalytic hydrogen evolution rate (HER) under visible light irradiation improved upon increasing the content of DBTO segment in donor–acceptor (D–A) structural polymers. Benefiting from the D–A structure and the high content of active centers of DBTO group, the polymer DB-Th displayed an unprecedentedly high HER of 334.50 mmol g−1h−1 under visible-light-driven and cocatalyst-free conditions (one of the most effective bare polymer photocatalysts that has been reported), which is 1.38-fold as that of the 2D–A type polymer with the lower DBTO content and 255-fold as that of the D–D structural polymer without DBTO segment, demonstrating the significance of acceptor content in D–A structures for achieving ultrahigh photocatalytic hydrogen evolution activity under visible light.